JPS6317445A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a multi-layered color photographic sensitive material having a large interimage effect without entailing an increase of fogging and the deterioration in particle characteristics and having high sharpness by incorporating specific compds. into a silver halide photosensitive material. CONSTITUTION:At least one kind of the compd. expressed by formula I and at least one kind of the compds. expressed by formulas II, III are incorporated into the silver halide photographic sensitive material. In formula, A is an oxidation-reduction base nucleus, an atomic group which permits elimination of -(Time)t-X when oxidized during a photographic development process, (t) is 0 or 1 integer, X is a development restrainer, R is an alkylene group, alkenylene group, aralkylene group, arylene group, Z is a polar substituent, Y is -S-, -O-, other prescribed groups, X' is -O-, -S-, other prescribed groups, R''' is a prescribed group such as alkylene group, Z' is H, polar substituent, Y' is -S-, other prescribed groups.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver oxide photographic material with increased fog (improved interimage effect, and improved sharpness). It is.

(Prior art) By color-developing a silver halide color photographic material, an oxidized aromatic-amine color developing agent and a coupler react to form indophenol, indoaniline,
It is known that indamine, azomethine, phenoxazine, phenazine and similar dyes can be produced to form color images. In this method, a subtractive color method is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, which has a relationship with the remaining colors, respectively.
Magenta, and cyan color image forming agents are used. To form a yellow image, for example, acylacetanilide or dibenzoylmethane couplers are used, and to form a magenta image, pyrazolone, pyrazolobenzimidazole, pyrazolopyrazole, pyrazolotriazole, cyano Acetophenone or indacylon couplers are used, and phenols or naphthols are primarily used to form cyan images.

By the way, the dyes produced from these couplers do not have ideal spectral absorption spectra (in particular, magenta and cyan dyes have a broad absorption spectrum or subabsorption in the short wavelength region, making them difficult to use in color photographic materials. Particularly, sub-absorption in the short wavelength range tends to lead to a decrease in saturation.One way to improve this is to develop an interimage effect to some extent. can.

As one means for improving this interimage effect, US Pat. No. 3,372. Juri issue, same J, A20,
No. 7444, same 4! , J77, A344, No. 33, No. 171, and JP-A-Kokai Akihiroter/2, J36.

These DIR hydroquinones release development inhibitors by being oxidized during the development process, but until now, DTEt hydroquinone has been shown to increase the rate of oxidation during the development process to improve the interimage effect. This has led to very serious problems in terms of photographic performance, such as increased fogging during the aging of the raw film and increased fogging during development. Conversely, if the reducing ability of DIR hydroquinone is lowered to a level that does not increase these fogs, the reducing power during the development process will be insufficient, and the release of the development inhibitor will be small (and the interimage effect will hardly be improved). I couldn't do it.

Also, the previously known US patent f, 2/Jlosr
No. 262μ776, No. 21 → 60! No. 2, 1
When a fog suppressant such as that disclosed in No. 27777 is used in combination with this DIR-hydroquinone, fog can be suppressed to some extent, but the interimage effect is also reduced due to the lowering of the developing activity of DIR-hydroquinone.

As described above, it has been extremely difficult to produce a large interimage effect without increasing fog caused by DIR hydroquinone. There has been a strong desire for a technology that can suppress the increase in fog caused by DIR hydroquinone while producing an interimage effect.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a multilayer color photographic material that has a large interimage effect without increasing fog.

A second object of the present invention is to provide a multilayer color photographic material that does not deteriorate graininess (has a large interimage effect) and has high sharpness.

A third object of the present invention is to provide
To provide a black and white silver halide photographic material with high sharpness and good graininess.

(Means for solving problems) The purpose of the present invention is to:

In a silver halide photographic light-sensitive material having at least / Jiii photosensitive silver halide emulsion layer on a support, at least seven kinds of compounds represented by the following general formula [I] and the following general formula (nJ This was achieved with a silver halide photographic material characterized by containing at least one compound represented by (l[[J).

General formula (I) A- (Time) Improve interimage effect.

By using these compounds in combination with the compound represented by the general formula (H), the increase in fog caused by the compound represented by the general formula (H) was suppressed, and surprisingly, the interimage effect was dramatically improved.

In place of compounds represented by the general formulas (IIJ and (IIIJ), U.S. Patent No. 2/J1031, U.S. Pat.
In the combination of the compound disclosed in ≠Hirotoj No. 2232707 and the compound represented by the general formula [I], fogging was suppressed, but the interimage effect caused by the general formula (H) was also reduced.

On the other hand, U.S. Patent No. J,! El, , Hiro? No. 6, No. 3, j3≦, No. 4417 discloses that diffusible thiazoline-2-thione improves the interimage effect. Even if this diffusible Hiro-thiazoline-2-thione is used in combination with a compound represented by the general formula (N), the increase in capri caused by the compound represented by the general formula (1) is suppressed, but the interimage effect is Instead of improving, it actually decreased slightly.

The general formula (A in IJ means a redox mother nucleus, and represents an atomic group that makes it possible for -
Time represents a timing group linked to A through a sulfur element, nitrogen atom or oxygen atom, t is an integer of 0 or l, and X means a development inhibitor.

Compound v3 of the general formula [IJ] used in the present invention will be explained below.

First, A in the general formula (N) will be explained in more detail. Examples of the redox nucleus represented by A include hydroquinone, catechol, p-aminophenol, 0-7 minophenol, l,2-naphthalenediol%/'1 μm naphthalene diol, l.

t-naphthalenediol, l,2-aminonaphthol,
1. Examples include p-aminonaphthol or IIi/, 6-aminonaphthol, and the like. At this time, the amino group has 1-2 carbon atoms! is preferably substituted with a sulfonyl group or an acyl group having -21 carbon atoms. Examples of the sulfonyl group include substituted or unsubstituted aliphatic sulfonyl groups and aromatic sulfonyl groups. Examples of the acyl group include substituted or unsubstituted aliphatic acyl groups and aromatic acyl groups. The hydroxyl group or amino group forming the redox core of A may be protected with a protecting group that can be deprotected during development. Examples of protective groups include those having 7 to 7 carbon atoms, such as an acyl group, an alkoxycarbonyl group, a carbamoyl group, and JP-A-Shoj et al.
．． OJ7, protecting groups described in JP-A-75'-201,0!7 are mentioned. Furthermore, this protecting group may be bonded to the substituents of A described below, if possible, to form j,
A 6° or 7-membered ring may be formed.

The redox nucleus represented by A may be substituted with an appropriate substituent at an appropriate position. Examples of these substituents include those having -2j or less carbon atoms, such as alkyl groups, aryl groups, alkylthio groups, arylthio groups, alkoxy groups, aryloxy groups, amine groups, amido groups, sulfonamide groups, cyclocarbonyl group, dicarbonyl group, carbamoyl & alkoxy dicarbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom, acyl group, carboxyl group, sulfo group, nitro group, heterocyclic residue, or +T I m e - to X, etc. These substituents may be further substituted with the substituents described above. These substituents may also be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle, if possible.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, 0-aminophenol, /,
Examples include French-naphthalenediol, /, and French-aminonaphthol. More preferred examples include hydroquinone, catechol, p-aminophenol, and 0-7i nophenol. Most preferred as A is hydroquinone.

Preferred examples of A in general formula (N) are shown below.

Note that in each structural formula, (*) indicates the position where +Time+tX is bonded.

H H (j) H H OH <r> OH OH OH (l-) OH OH (/da) OH OH OH (/I) α (lli) OH (koO) OH * (λl) OH (JJ) Nl food 502CH3 H (2IA) OH OCl 4829 (n) TimeX is e + Timex only when the redox nucleus represented by A in the general formula CI) undergoes a cross-oxidation reaction during development and becomes an oxidized product. It is a group released as -Xl.

Time is a timing group that connects to A with a sulfur atom, nitrogen atom, or oxygen atom, and e4- released during development.
Examples include groups that release X from Time-)-X through one or more reaction steps. As Time, for example, US Pat.

No. 42, U.S. Patent No. 323, British Patent No. 4.713, U.S. Patent No. μ.

tut, No. 396, Publication No. J/-/1A4.12, Publication No. 17-44. Examples include those described in rJ7. Time may be a combination of two or more selected from those listed above.

The timing group represented by Time in general formula (I) is particularly preferably one represented by the following general formula. Here * represents the site where the redox nucleus binds,
** represents the site where PUG binds. Time may be a combination of two or more of the following.

General formula (T-/) represents 10-1-S-1-8-CH2-1-S-C-1 or -he-C-. Here, R31 is a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.

Xl represents a hydrogen atom, an aliphatic group, an aromatic group, a nitro group spanning a heterocyclic ring (eg, fluorine, chlorine, bromine, iodine).

Here, R32 and It33 may be the same or different and represent the group described for R31.

X2 represents the group described for R31.

q represents an integer from / to μ. When q is 2 or more, %X1
The substituents represented by may be the same or different. q
When is 2 or more, Xl may be linked together to form a ring.

p represents o, i or -2. r represents O or l.

The group represented by the general formula (T-/) is, for example, U.S. Patent No. ≠, coφ? , No. 62.

General formula (T--2) In the formula, Zl, XI%X2, and Qsr have the same meanings as defined in the general formula (T-/).

General formula (T-j) *-z2-(C)12J-N-C-(OCH2), -
**Represents ko. m is an integer from 1 to Hiroshi, preferably l.

or 3. R31, X2, and r have the same meaning as defined in the general formula (T-/).

General formula (T-Hiroshi) lag Wasu. Here, R36 is an aliphatic group, an aromatic group, an acyl group,
Represents a sulfonyl group or a heterocyclic group. R34, Ras
#2 Represents the same meaning as R31 defined in general formula (T-/). Xl and q have the same meaning as defined in the general formula (T-/).

The group represented by the general formula (T-Hiroshi) is, for example, a timing group described in US Pat.

In the formula, za s Consisting of at least one or more atoms selected from j-membered ~7
It is an atomic group necessary to form a member heterocycle. This heterocycle may further be fused with a benzene ring or a 5-membered or above-mentioned heterocycle. Preferred heterocycles include, for example, pyrrole, pyrazole, imidazole, triazole, furan, oxazole, thiophene, thiazole, pyridine,
Examples include pyridazine, pyrimidine, pyrazine, azepine, oxepine, indole, benzofuran and quinoline. R34% R35, Z3, X 11q
represents the same meaning as defined in the general formula (T-Hiroshi). The group represented by the general formula (T-4) is, for example, described in British Patent No. 2. This is a tiling group as described in No. 713.

In the formula, X5 is an atomic group consisting of at least one or more atoms selected from carbon, nitrogen, oxygen, or sulfur, and is necessary to form a j- to 7-membered heterocycle. X6
and X7 is -C= or to bar=. Here, R37 represents a hydrogen atom, an aliphatic group, or an aromatic group.

This heterocycle may further be fused with a benzene ring or a Fij- to 7-membered heterocycle. Preferred heterocycles include:
Examples include pyrrole, imidazole, triazole, furan, oxazole, oxadiazole, thiophene, thiazole, thiadiazole, pyridine, pyridazine, pyrazole, zine, pyrazine, azepine, oxepine and inquinoline. R34, R35, Z3,
xlsq represents the same meaning as defined in general formula (T-4').

General formula (T-4) In the formula, XIO consists of at least one or more atoms selected from carbon, nitrogen, oxygen, or sulfur, and has j-membered to
It is an atomic group necessary to form a 7-membered heterocycle. X8 and X9 are -C= or to one. This heterocycle may further be fused with a benzene ring or a j- to 7-membered heterocycle.

Preferred heterocycles include, in addition to those listed in general formula (T-6), pyrrolidi/, biylidine, benzotriazole, and the like.

Zl, XI, X2, n and qr have the same meanings as defined in general formula (T-1).

General formula (T-ta) In the formula, % X 11 is XI defined in general formula (T-r)
It has the same meaning as O. z3 has the same meaning as defined in the general formula (T-Hiroshi), and ノ represents O or l. Xl
Examples of preferable heterocycles for l include those shown below.

Here, Xl and q have the same meaning as defined in the general formula (T-/), and X12 is a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, a sulfonyl group, an alkoxy carbonyl group, a sulfamoyl group. , represents a heterocycle or a carbamoyl group.

General formula ('1'-1o) "In the formula, x1%X2 is the general formula (T-/), and Z3 represents the same meaning as defined in the general formula (T-4').m is the general formula It has the same meaning as defined in (TJ), and is preferably l or co.

From the above general formula (T-/) to ('l'-70), %
When XI, X2%R31. to 1137 contains an aliphatic group moiety, it preferably has 7 to 20 carbon atoms, and may be saturated or unsaturated, substituted or unsubstituted, chain or cyclic, straight chain or branched. Possible 0 above X1
s When X2 and R31 to R37 contain an aromatic group, the number of carbon atoms is 6 to 20°, preferably 6 to 10,
More preferred is a substituted or unsubstituted phenyl group. When xl, X2, R31 to R37 contain a heterocyclic group, it is a j- or t-membered heterocyclic ring containing at least 7 nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms. Preferred heterocyclic groups include pyridyl, furyl, chenyl, triazolyl, imidazolyl, pyrazolyl, thiadiazolyl,
It is a diazolyl group or a pyrrolidinyl group.

Preferred timing groups are, for example, those shown below.

<i> 2Hs 2H5 (″) COC) 13 (7] <r) *-8-(CH2) 2-N-C-**CH(CHa)
2 - to O2 0x Nhs02c83 C)12-** (λ0) * (λj) * (2A) *2 H5 *-8 (2g) *C)i(CH3)2 * (33) (j4A) (3j
) to CO)i3 *-N-C)l-** *-8-C)12-N-C)12-**CH3 (3t) (3ri) (uO) c2H,.

(≠l) X means a development inhibitor. Examples of development inhibitors include:
Examples include compounds having a mercapto group bonded to a heterocycle or heterocycle compounds capable of producing iminosilver.

Examples of compounds having a mercapto group bonded to a heterocycle include substituted or unsubstituted mercaptoazoles (e.g. /-phenyl-!-mercaptotetrazole, /-propyl-j-mercaptotetrazole, i
-butyl-j-mercaptotetrazole, λ-methylthio j-mercapto F / + 3+ "-thiadiazole, 3-methyl-hiro-phenyl-mercapto 7
．． Co, μ-triazole, /-(Hiro-ethylcarbamoylphenyl 1,2-mercaptoibadazole, -mercabutobenzoxazole, comelcabutobenzimidazole, comelcabutobenzothiazole, 2-mercabutobenzoxazole, cophenylated !-Mercap)-/.

3. P-oxadiazole, /-(J-(J-methylureido)phenyl)-! -Mercaptotetrazole, /
-(μ-nitrophenyl)-j-mercaptotetrazole, 2-(coethylhexanoylamino)-comelcabutobenzimidazole, etc.), substituted or unsubstituted mercaptoazaindenes (for example, 6-methyl-Hiro- Mercapto/, J, Ja, 7-chitrazaindene,
-1t-dimethyl-mercapto'*' e
' a *7-titrazaindene, etc.), substituted or unsubstituted mercaptopyrimidines (eg, komelkabutopyrimidine, komelkabuto≠-methyl-1-hydroxypyrimidine, etc.).

Imino 57fI: As a heterocyclic compound that can be formed,
For example, substituted or unsubstituted triazoles (e.g. %
/1co, 4c-triazole, benzotriazole, j
-methylbenzotriazole, j-nitrobenzotriazole, s-7' lomobenzotriazole, j-n-butylbenzotriazole, J, t-dimethylbenzotriazole, etc.), substituted or unsubstituted indazoles (for example, inta:/ "-A/, j-nitrointasole, 3-nitrointasole, J-chloro-y-nitroindazole, etc.), substituted or unsubstituted benzimidazoles (e.g.!-nitrobenziidazole, 3-nitrointasole, etc.),
．． 6-cyclobenzimidazole, etc.).

In addition, X is a general formula (separated from Time of N.

Once it becomes a compound that has development inhibiting properties, it undergoes a certain chemical reaction with the developer components and changes into a compound that has substantially no or significantly reduced development inhibiting properties. Good too. Examples of functional groups that undergo such chemical reactions include ester groups, carbonyl groups, imino groups, immonicum groups, Michael addition-accepting groups, and imide groups. Examples of such deactivated development inhibitors include I-(3-] dicarbonylphenyl-monomercaptotetrasol s'(''-phenoxycarbonylphenyl)-!
-Mercaptotetrazole, / -(3-maleinimidophenyl)-! -Mercaptotetrazole, j-7 dinopairodicarbonylbenzotriazole, j-(μm cyanophenoxycarbonyl)incitriazole, 7 carbonylmethylthio in cofeno! -Mercapto-/,
3゜Hiro - Thiadiazole! - dicarbonyl 3-dicarbonylimidazole%j-(co,3-dichloropropylene dicarbonyl)benzotriazole, /-(U
-diphenyl in penzoyl)-! -Mercaptotetrazole, j-(2-methanesulfonylethodicarbonyl)-2-mercaptobenzothiazole, j-cinnamoyl abanobenzotriazole, 1-(J-vinylcarbonylphenyl)-y-mercaptone 5"/-l, j
-succinimidomethylbenzotriazole, -1 (succinimide is dophenyl) -j-mercapto-/, j
, ≠-Ono-Sadiazole, Roofenoxycarbonyl-comel-kabutobenzo-Zol, and the like.

In order to describe the content of the present invention in more detail, examples of the compound represented by the general formula (1) are shown below.

However, the compounds that can be used in the present invention are not limited to these.

(■-λ) C4Hg (I-φ) (1-1) (1-73(1-r) (■-ta) H (1--tj) OH The compound represented by the general formula (I) is In general, it can be synthesized in the following two ways. First, Time is a simple bond (t
= 0), the first is in chloroform, l, λ-dichloroethane, carbon tetrachloride, or tetrahydrofuran without catalyst or in the presence of an acid catalyst such as p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. Below are benzoquinone, orthoquinone, quinone monoimine, quinone diimine derivatives, and development inhibitor +Iil.
This is a method in which the agents are reacted at temperatures between room temperature and ioo 0c. λ is a benzoquinone, orthoquinone substituted with chlorine, bromine or iodine, in the presence of a base such as potassium carbonate, sodium bicarbonate, sodium hydride or triethylamine in an aprotic polar solvent such as acetone, tetrahydrofuran or dimethylformamide; quinone monoimine, quinone diimine derivative and development inhibitor
This is a method in which a quinone compound obtained by a reaction between 00C and ioo'c is reduced with a reducing agent such as diethylhydrocytylamine or sodium hydrosulfide.

(Reference: Re5earch Disclosure
e/r427 (/ri7ri); Liebigs A
nn, Chem.

7, lJ/(/ri7con) Then X is released via Time (t=/)
can also be synthesized in almost the same manner as above. In other words, Time-X is used instead of the above development inhibitor (X), or Ti having an XK substitutable group (e.g., a halogen atom, a hydrocarbon group, or a precursor thereof)
This is a method in which me is first introduced into a redox core, and then X is linked by a substitution reaction.

The compound represented by the general formula (N) may be added as an emulsion obtained by dissolving in high-boiling oil and stirring at high speed, or by adding it to a gelatin solution dissolved in a water-soluble organic solvent such as alcohol or Cello 7 Lube with stirring. It may be added in finely dispersed form.

In the general formula (IIJ, R represents a straight-chain or branched alkylene group, a straight-chain or branched alkenylene group, a straight-chain or branched aralkylene group, or an arylene group,
zFi represents a polar substituent. Y is R5, R6, R7, R
8, R9 and RIG are each a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkenyl group,
represents an aralkyl group R'. X' represents 10-1-h or -S-, and R represents a hydrogen atom or a substituted or unsubstituted alkyl group or alkenyl group, respectively.

R" represents a hydrogen atom or a group that can substitute this.M
represents a hydrogen atom, an alkali metal atom, an ammoniamyl group, or a group that cleaves under alkaline conditions. n represents O or l; m represents 0, l or -. However, %
When ' is -S-, m=.

is not included. l represents μ-m.

More specifically, R is a linear or branched alkylene group (
For example, methylene group, ethylene group, propylene group, methylene group, etc. 7 ren group, /-methylethylene group, etc.)
, linear or branched alkenylene 4 (e.g. Lk'!, vinylene group, l-methylvinylene group, etc.), linear or branched aralkylene group (e.g. benzylidene group, etc.), arylene group (e.g. phenylene, naphthylene group, etc.) , etc.).

Examples of the polar substituent represented by Z include substituted or unsubstituted amino groups (including salt forms, such as amino groups, hydrochloride of amino groups, methylamino groups, dimethylamino crystals, hydrochloric acid of dibutylamino groups) salt, dibutylamino group,
Dipropylamino group, N-dimethylaminoethyl-N-
methylamino group, etc.), quaternary ammonylamyl group (e.g., trimethylammonylamyl chloride group, dimethylbenzylammonyl chloride group, etc.), alcohol-+'
groups (e.g., methoxy group, ethoxy group, cohydrobutylthio group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkylthio group (e.g., methylthio group, butylthio group, etc.), arylthio group (e.g., methylthio group, butylthio group, etc.) For example, phenylthio group, etc.), heterocyclic oxy group (e.g., cobiridyloxy group, λ-imidazolyloxy group, etc.), heterocyclic thio group (e.g., 2-benzthiazolylthio group,
Hiro-virazolylthio group, etc.), sulfonyl group (e.g.
methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (e.g., evaporation, unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl & (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, etc.), moyl group, etc.), carbonamide group (e.g. acedoyl group, benzamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (e.g. acyloxy group, benzoyloxy group, etc.), ureido group (
For example, unsubstituted ureido group, methylureido group, ethylureido group, etc.), acyl group (for example, acetyl group,
benzoyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), thioureido group (e.g., unsubstituted thioureido group, methylthioureido group, etc.), sulfonyloxy group (e.g., methanesulfonyl 7 group, p-toluenesulfonyloxy group, etc.], heterocyclic groups (e.g., l-morpholino group, !-piperidino group, -1-pyridyl group, di-pyridyl group, cochenyl group, l-pyrazolyl group, l-imidazolyl group, λ −
Examples include an imidazolyl group, a cochtotrahydrofuryl group, a cochtotrahydrochenyl group, etc.), and a hydroxyl group.

R1% 12% R3, R4% R5% R6% R7, R8
, R9 and RIG are hydrogen atoms, substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, propyl group,
codimethylanoethyl group, etc.), substituted or unsubstituted aryl groups (e.g., phenyl group, comethylphenyl L, etc.), substituted or unsubstituted alkenyl groups (e.g., propenyl group, l-methylvinyl group, etc.), Alternatively, it represents a substituted or unsubstituted aral group (eg, benzyl group, phenethyl group, etc.).

R' is a hydrogen atom or a substituted or unsubstituted alkyl group (
For example, methyl group, ethyl group, propyl group, cordimethylaminoethyl group, 2-hydroxyethyl group, 2-imidazolylethyl group, cordimethylaminopropyl group, etc.), substituted or unsubstituted alkenyl group (for example, propyl group), (M, /-methylvinyl group, etc.).

Further, R represents a hydrogen atom or a group that can be substituted for this, and examples of the substitutable group include a halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom, etc.) Number of carbon atoms/-
4, substituted or unsubstituted alkyl group (e.g. methyl group, trifluoromethyl group, ethyl group, n-butyl group, etc.)
, a substituted or unsubstituted aryl group having from 1 to 12 carbon atoms (
For example, phenyl group, μm methylphenyl group 1, carbon i number l
-1 substituted or unsubstituted alkoxy group (for example, methoxy group, ethoxy group, etc.), carbon number 4. -/co substituted or unsubstituted aryloxy group (e.g., phenoxy 7 group,
μm methylphenyl group, etc.), sulfonyl group with carbon number i-i (e.g. methanesulfonyl group, p-1 luenesulfonyl group, etc.), sulfonamide group with carbon number /~/co (e.g. methanesulfonamide group, p -toluenesulfonamide group, ethanesulfonamide group, etc.), sulfamoyl group having 7 to 7 carbon atoms (e.g. diethylsulfamoyl group,
phenylsulfamoyl group, etc.), carbamoyl group with carbon number /-/co (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), carbon number 2 to
72 amide group (e.g. acetamide group, benzamide group, etc.), carbon number /-/co ureido group (e.g. unsubstituted ureido group, 3-methylureido group, 3-phenylureido group, etc.), carbon number -/co aryl or alkoxy group (e.g., methoxycarbonyl group, phenoxycarbonyl group, etc.), carbon a, 2-12 aryl or alkoxy carbonyl group (e.g., methoxycarbonyl group, phenoxycarbonylamino group, etc.)
, cyano group.

M is a hydrogen atom, an alkali metal atom (e.g., sodium atom, potassium atom, etc.), an ammoniayl group (e.g., trimethylammonylamyl chloride group, dimethylbenzylammonylamyl chloride group, etc.), or under alkaline conditions, X= Represents H or a group that can be an alkali metal (eg, acetyl group, cyanoethyl group, methanesulfonylethyl group, etc.).

In the general formula (IIJ, preferably R is a substituted or unsubstituted alkylene group, Y is -C-N-1R6, R7 is a hydrogen atom, X' is -NH- or -0-1Z is a substituted or unsubstituted amino group) or a salt thereof, or a heterocyclic group.

Specific examples of the compound represented by the general formula (I[) are listed below, but are not limited to these. ) (■-ta) (n-20).

(■-λhiro) (■-2j) ([-2y) (■-kot) (■-Kota) ■ (If-JO).

(II-J/) (l[-Jko) (■-3μ) (II-31 (■-3≦) (II-37) (n-
Jr) (n-jri] (■-see〇) C)12cH20)1 The compound represented by the general formula (n) used in the present invention (
Organic Nonsense) OrganicSynth
esis, ■, j6ri(/ri”); (Journal of the American Chemical Society) Jou
rnal of the AmericanCh
emical 5ocity, 4' j *ko JY
O (/ri JJ); (Chemis S-Berichte) Chemis
It can be synthesized according to cheBerichte, ri, g4r(/f74), etc., or the typical synthesis examples shown below.

Synthesis Example 1 Synthesis of Exemplified Compound (n-/) j-Aminocomercaptobenzimidazole JA, 6p and pyridiy/7,/++jKN, N-dimethylacetamitocojOml were added, and phenylchloroformate 34c was added at room temperature. , 4! y was added dropwise. After stirring for i and z hours at room temperature, 1. When added to J, crystals precipitated.

The obtained crystals were separated and recrystallized from acetonitrile to obtain -1 mercapto! -Dicarbonylaminobenzimidazole 1 L7.7.9 in Funino was obtained.

The resulting Komel Kabuto! - Phenoxycarzenylaminobenzimidazole t, 6 g to acetonitrile 10
Add 0ml of N,N-dimethylaminoethylenediamine lIA to the mixture and heat with stirring.

19 was added dropwise. After stirring at μj 'C for i and z hours and collecting the precipitated crystals, recrystallization was performed from a mixed solvent of N,N-dimethylformamide and methyl alcohol to obtain the target products 4, J, 9 (yield: 7 h). Obtained.

Melting point 2≠O'C (decomposition) Synthesis example 2 Synthesis method of exemplified compound (II-//) Synthesis example 1
Cormel Kabuto J-phenoki 7carbonylaminobenzimidazole/4C obtained in .

Add 100rnl of ethyl alcohol to 3g, and heat at room temperature.
-N,N-dimethylaminopropylamine was added dropwise.

After dropping, stir at μ0°C for 2 hours, then add 1o acetonitrile.
When ornt was added, crystals were precipitated.

The precipitated crystals were recrystallized twice with a mixed solvent of N,N-dimethylformamide and acetonitrile to obtain the desired product 7.
．． 29 (yield Zettatin) was obtained.

Melting point: 2r06C or higher (decomposition) Synthesis Example 3 Synthesis of Exemplary Compound (It-4) 2-Mercap)-j-phenoxycarbonylaminobenzimidazole/Hiro obtained in Synthesis Example 1.

Add 100 tl of ethyl alcohol to Jli and add 3-
Morpholinopropylamine If and 7Iif were added dropwise.

After the dropwise addition, 3 g of the mixture was stirred at JO'c, and then cooled to room temperature to precipitate crystals. The precipitated crystals were collected and recrystallized from a mixed solvent of N,N-dimethylformamide and acetonitrile to obtain 4.7 g (yield: 4 cλ) of the desired product. Melting point ro 0g or more (decomposition) Synthesis example 4 Exemplary compound (I
N,N-dimethylformamide rorttt was added to 6-carboxy 2-mercaptobenzothiazole/2.69 of t--27), and triethylamine/J was added under water cooling.

6141 was added dropwise, and then 1 liter of ethyl chloroformate was added.

6- was added dropwise. After stirring for 30 minutes under water cooling, comethanesulfonamidoethylamine P was added.7. p was added dropwise, and the mixture was stirred for a long time. After adding the reaction solution to ice water/E and collecting the precipitated crystals, they were recrystallized from ethyl alcohol to obtain the target product lλ.
,/,? (Yield 4/%) was obtained. Melting point 2 ko 2 ~ ko reference a
OC Synthesis Example 5 Synthesis method of exemplified compound (If--1F) p-(
To a solution of 2.4 Ag of potassium hydroxide in ethyl alcohol, 7.19 g of N,N-dimethylaminoethoxy)-〇-phenylenediamine was added, and carbon disulfide/JjL/ was added dropwise at μ0°C.

After the dropwise addition, the mixture was heated under reflux for 3 hours, and after adding salt preparation j[d, the solvent was distilled off under reduced pressure. The obtained oily residue was purified with a silica gel column and then recrystallized from acetonitrile to obtain the desired product 3.
19 (yield uoqb) was obtained.

Melting point -2JJ~23! oC (Decomposition) Synthesis Example 6 Synthesis of Exemplified Compound (It-/J) Komelkabuto-6-phenoxycarbonylaminobenzoxazole/7. synthesized in the same manner as Synthesis Example 1. Add ethyl alcohol to λI and prepare N,N-dimethylethylenediamine A, 2i at room temperature.
f was added dropwise. After stirring at vk100C for 30 minutes, crystals were precipitated when the mixture was cooled to room temperature. The precipitated crystals were collected and recrystallized from a mixed solvent of N,N-dimethylformamide acetonitrile to obtain target products IJ and J9 (yield: 7 ml).

Melting point λto''c or higher (decomposed) General formula (l[In IJ, R'' represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group, Z/ represents a hydrogen atom or a tetrapolar substituent .Y' is -8, Rlz R13R14
FLls represents %R11%R12% FL13%R14%FL
1s s Rts, R17 or R18 represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or an aral group. M represents a hydrogen atom, an alkali metal atom, an ammoniamyl group, or a group that cleaves under alkaline conditions. n represents O or /.

More specifically, R# is a straight or branched fullkylene group (e.g., methylene group, ethylene group, propylene group, butylene group, silane group, l-mef /I/!?ren L, etc.), Chain or branched alkenylene groups (e.g., t, hynylene, /-methylvinylene, etc.), straight or branched aral groups (e.g., indylidene, etc.), arylene groups (e.g., t, hynylene, /-methylvinylene, etc.); , phenylene, naphthylene, etc.).

The polar substitution group represented by 2' is, for example, a substituted or unsubstituted amino group (including salt form, for example, ai
) group, hydrochloride of amino group, methylamino group, dimethylamino group, hydrochloride of dimethylamino group, dibutylamino group, dibutylamino group, h-dimethylanoethylhemethylamino group.

etc.), quaternary ammonyl bal groups (e.g., trimethylammonyl chloride group, dimethylbenzylammonyl chloride group, etc.), alkoxy groups (e.g., meth
groups, etho Φ7 groups, λ-metho groups, etc., aryl groups (e.g., 7 groups in pheno, etc.), alkylthio groups (e.g., methylthio groups, butylthio groups, etc.),
Arylthio groups (e.g. phenylthio group, etc.), heterocyclic thio groups (e.g. λ-pyridyl group, 2-imidazolyl group, etc.), heterocyclic thio groups (e.g.
Cobenz thiazolylthio group, μm virazolylthio group 1
etc.), sulfonyl groups (e.g. methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl L, etc.), carbamoyl groups (e.g. unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl groups (e.g. unsubstituted sulfamoyl group) , methylsulfamoyl group.

), carbonamide group (e.g., acetamide group, indusamide group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, etc.)
, alkoxy groups (e.g., acetyloxy group, benzoyloxy group, etc.), ureido groups (e.g., unsubstituted ureido group, methylureido group, ethylureido group, etc.),
Anru group (e.g. acetyl group, benzoyl group, etc.),
Aryloxycarbonyl & (e.g., phenoxycarbonyl group, etc.), thiourido group (e.g., unsubstituted thioureido group, methylthioureido group, etc.), sulfonyloxy group (e.g., methanesulfonyl group, p-1)
), heterocyclic groups (e.g. l-morpholino group, l-bilysino group, 2-pyridyl group, μm pyridyl group, coachenyl group, l-pyrazolyl group, λ-imidazolyl group, 2 -tetrahydrofuryl group,
(cochintrahydrochenyl, etc.), cyano group or a'r
f be beaten. Here, 2 represents a sulfonic acid group, a carzenic acid group, a toro-oxygen group, and an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group,
etc.).

When representing R11, R12, R13, R14, R1
5, R16, R17 or Rlg is a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, propyl group, λ-dimethylaminoethyl group, etc.),
Substituted or unsubstituted aryl group (e.g. phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (e.g. propenyl group, l-methylvinyl group, etc.), or substituted or unsubstituted alkenyl group (e.g. propenyl group, l-methylvinyl group, etc.) Aral represents an aral group (eg, benzyl group, phenethyl group, etc.).

Specific examples of the compound represented by the general formula (1) are shown below, but the compounds of the present invention are not limited thereto.

(III-/) (■-λ) (1-j) (■-Hiroshi) ([1-j) (III-4) (III-7) (III-r) (■-2) (III-/ Q) (In-//) (m-12) (III-/j) (■-/Hiroshi) ([1-/ri(m-il) (III-/7) (m-/I) ( lll-/ri) ・Sho (■-kol) ・-rul (■-kon2in (■-23) (■-λ≠) (■-λyo) (■-26) (■-27) (■-Kol) (■-Kota) (III-JO) ・Hα (III-JJ) ([1-JJ) ・Toa (III-JJ) (■-3μ) (l1l-J j ) (I [[-36) (III-37) <m-31) (■-3ri) (m-da0) (■-≠/) (■-μs) (■-μhiro) (■-sanj) (■-Referencet) (1-4'7) (■-μr) α0 (■-Hirori) (III--90) (III-j/) h (In-j ko) (l[I-j j ) (I[I-jμ) (lll-7yo) (III-54) (III--t7) (n[--tr) (II-jri) (III-go) (III-4/) (III-Ako) (III-47) (■-Buda) (In-Haruka!) The compound represented by the general formula (III) used in the present invention is a compound represented by 1 Adoptions in Heterocyclic Chemistry ( Advances 1nHeterology
clic Chemistry)', Volume 1.

Pages 74j to 20 (1st 6th year), 1st journal.
Journal of Pharmace
uticalSociety Japan)'+No. 7
It can be synthesized by referring to Spring 23, No. 201.

Also, Y' represents a ureido group or a thioureido group: -Mercapto i, s, a Reacting incyanates and inthiocyanates with i, s, a-thiadiazole, or mercapto! -Phenoxycarbonylamino-1, J. It can be easily synthesized by reacting thiadiazole with amines.

A practical example of synthesis is shown below.

Synthesis example/Synthesis method of compound (III-/) λ,! -dimercapto-7,3,≠-thiadiazole7,7? ,
Coraminoethyl chloride hydrochloride/ rt,
Pyridine 449 was added to n-butanol 449 and heated under reflux for several hours. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration and recrystallized from methanol/water. Yield 7. /S'
Melting point r~kokota °C (dec) Synthesis example ko Synthesis method of compound (III-/l) ko,! -Dimercapto-/,! , 44-thiadiazole 7#f, 2
-dimethylaminoethyl chloride hydrochloride 7,3?
, 4 Ltfn-butanol and 60 g of pyridine were added, and the mixture was heated under reflux for 2 hours. The reaction solution was cooled with water, and the precipitated crystals were collected by filtration and recrystallized from ethanol. Yield 7. rit Melting point lbu/~/A11C Synthesis example J Synthesis method of compound (11-/J)-,! −
dimercapto/, J, II-thiadiazole 7,! f
S2-diethylaminoethel chloride hydrochloride r,
ap, pyridine pP'In-butanol totxt and heated under reflux for 2 hours. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration and recrystallized from ethanol/water. Yield 10
．． /l Melting point lIμ~/ra”c Synthesis example da Synthesis method of compound (III-J), !-dimercapto-1,!, 4cm thiadiazole 7, It,!
-Dimetelaminoglovir chloride hydrochloride 7.2t1
Pyridine 4cft-n-butanol 40rd plus 2
The mixture was heated to reflux for an hour. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration and recrystallized from ethanol. melting point/
11C Synthesis Example I Compound <m-4c, 2> and (III-4'
Synthesis method of J)■ Synthesis method of Co(N,N-bis(Comethoxycarbonylethyl)aminocoethyl chloride hydrochloride Coaminoethanolj, /P with methanol 7!rdK
In addition, 20 ytl of methyl acrylate was added dropwise while cooling with water. After the dropwise addition, the mixture was stirred for an hour while cooling with water, and further stirred at room temperature for 20 hours. To the oil (JjP) obtained by evaporating the reaction solution under reduced pressure, 7rxlt of thionyl chloride was added dropwise to the oil (JjP) under ice cooling, and then heated under reflux for 1 hour. The reaction solution was distilled off under reduced pressure, and the resulting residue was recrystallized into Improper Tool/N-. Yield: 21f Melting point: 10J-10C■ Synthesis method of compound (III-4') 2,! -dimercaptothiadiazole 7,7
? .

Co(N,N-bis(comethoxycarbonylethyl)
Aminocoethyl chloride i4c, 4tt, pyrimidine! ,/? was added to Geosan tOd and heated under reflux for 2 hours. The reaction solution was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography (stationary phase alumina, developing solvent methanol/
By purifying with ethyl acetate), the compound (■-Hiroko)
was obtained as syrup. Yield tr, ≠ 2 ■ Synthesis method of compound (In-4'j) 7.3f of compound (II-4'-2) was added to 20xl of aqueous sodium hydroxide solution and stirred for 1 hour at to'c. . 3 while cooling the reaction solution on ice! The precipitate produced by neutralization with dihydrochloric acid was collected by filtration and recrystallized from DMF/ethanol to obtain compound (III-4'J). yield! ,2
9 Melting point try ~irt'c synthesis example t Compound (■
-μ) synthesis method 1, Tajmercapto-/,! ,'A-thia'diazole/j,Of,sodium methoxytocorrtisol Q
JO was added to 100 g of ethyl alcohol and dissolved by heating, and Coke Chlorethyl Urea/J and IP were added dropwise. After the dropwise addition, the mixture was heated to reflux for an hour. After the reaction, add 700ml of ice water to the reaction solution.
The precipitated crystals were collected by F and recrystallized from methanol. Yield/A, ≠2 Melting point 17 da~/74 °C Synthesis Example 7 Synthesis method of compound (■-2)/! 1 of t. ! - Dimercapto/, J, add one thiadiazole to 300rd acetone, then 2-
Two volumes of β-chlorpropionamide were added to each liter of a 2R% solution of sodium methoxydide.

Furthermore, sodium iodide/jft'' was added to this reaction solution,
The mixture was heated under reflux for 20 hours. After cooling, the obtained crystal f:P was collected and washed with water. The crystals were recrystallized from a mixed solvent of dimethylformamide and methanol, and the compound vrt<m-a>'i
It was. MXfik/2. Of melting point /73~/77°
C Synthesis Example t Synthesis method of compound <m-tap)! -Dimercapto-/,! , 4L-thiadiazole/! j, 0?
, no(chloroethyl)imidazole hydrochloride co0.
Of, Piridinta! t to 100 m of acetonitrile
1 and heated to reflux for μ hours. After the reaction, the reaction solution was cooled, and the precipitated crystals were collected and recrystallized from a mixed solvent of dimethylformamide and methanol to obtain compound Cm4.

Yield//, if Melting point JJj-2kr ``C Synthesis example ta Method for preparing compound <m-at> Add 200 g of acetonitrile to comercapto!-phenoxycarbonylamino-1,32 μm thiadiazole/2.7f at room temperature.
-N,N-dimethylaminopropylamine was added dropwise. After the dropwise addition, the mixture was heated and stirred for 1.1 hours using a jo"c, and the precipitated crystals were collected and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain a compound (■-≠).

Yield: 10.7f Melting point: 2t~3o'c Synthesis Example 1
0 Synthesis method of compound (III-4'4) - monoamino! -Mercapto-/13. ≠-thiadiazole/3. J
Dissolved in 100 d1 of ff acetonitrile and 4 co- of dimethylacetamide, and at room temperature J-(N,N-dimethylamine)propyl inthiocyanate 1! ,the law of nature? was dripped. After the dropwise addition, the mixture was heated and stirred at 20° C. for several hours, and the precipitated crystals were collected and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain a compound (■-μ4). Yield 12.4f Melting point l da t ~ / Hiro @C Synthesis example // Synthesis method of compound (!O) λ-Mercapto! -phenodP7 carbonylamino/,! , 4cm
Thiadiazole/, 2.7r to ethyl alcohol 100%
Add d and add 3-morpholinopropylamine lr, 7 at room temperature.
ff was dropped. After the dropwise addition, the mixture was stirred at a moderate temperature for 1 hour to precipitate nine crystals, which were recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain the compound <Jo>t-. Yield #L10.9? Melting point! ! ~-! 76C When the compounds represented by the general formulas (1), (If) and (III) of the present invention are used in a multilayer color photographic light-sensitive material, a silver halide emulsion layer or a yellow filter layer adjacent to the emulsion layer, an anti- It is contained in at least one layer such as a halation layer, an intermediate layer, or a protection layer, but it is preferably contained in a silver halide emulsion layer or an intermediate layer adjacent to the emulsion layer.

Furthermore, when applying the present invention to black and white photographic materials,
The compounds represented by the general formulas [l], (It) and (III) are contained in the silver halide emulsion layer and/or the retention layer.

The compounds of the present invention represented by general formulas (1), (If) and (1) are generally used in the same layer or in adjacent It is l~/0-'' mole per mole of silver halide present in the layer, preferably JXlo
-"~j X/0'""4.

In order to introduce the compounds represented by the general formulas (n) and (In) of the present invention into a photographic material, water, methanol, ethanol, glopanol, or fluorinated alcohol is commonly used in the photographic material. After dissolving in the solvent used, it is added to the hydrophilic colloid. When included in the silver halide emulsion layer, when forming grains of the silver halide emulsion,
During physical ripening, immediately before chemical sensitization, during chemical sensitization, after chemical sensitization,
Alternatively, it may be used at the time of preparing the coating solution, and is selected depending on the purpose.

The compound represented by general formula CI) and the compounds represented by general formulas (n) and (1) may be added in the same layer or in different layers, but may be added in the same layer or in different layers. , is preferably added into the adjacent layer.

The photosensitive materials to which the present invention is applied include, for example, color negative film, color reversal film (inner mold and outer mold), color base/color film, color positive film, color reversal paper, color diffusion transfer process, color photographic photosensitive material such as die transfer process, etc. The photosensitive material may be any of black and white photographic materials such as black and white negative film, black and white photographic paper, X-ray film, and lithographic film.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide, including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and iron chloride, may be used. The preferred silver halide is silver iodobromide or silver iodochlorobromide containing less than about 30 moles of silver iodide. Particularly preferred is silver iodobromide containing from about O1 to about 10 moles of silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. Also, mixtures of particles of various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 < microns or less, large grains with a projected area diameter of about 10 microns, monodispersed emulsions with a narrow distribution tW, or polydisperse emulsions with a wide distribution. A dispersed emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 17, Mu/74≠3 (/ri 7 in February 2007), 22-
23 pages, Emulsion Pre
Paratlon and Types)” and the same, vol. 117, A/17/lC/77/972), t
You can follow the ar page Senior July method.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimle et Ph
yslquePhotographique Pa
ul Montel,/ta-[7],
"Photographic Emulsion Chemistry" by Duffin, Focal Press 4th edition (
G, F, Duf in, Pholog
raphlcEmulsion Chemistry
(Focal Press.

/ P j j ), Zelikman et al., "Production and coating of photographic emulsions", Focal Press 4th issue ('V, L,
Z+611krnanat if, Making
and Coatlng Photo-graphic
Emulsion, Focal Press.

It can be prepared using the method described in (1999), etc. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Good too. A method in which grains are formed under an excess of silver ions (the so-called back-mixing method>1 can also be used. One type of simultaneous mixing method is a method in which pA g f in the liquid phase in which silver halide is formed is kept constant. That is, the so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Also known silver halide solvents such as ammonia, Rodankali or US Patent MJ, Core/.

No. 777, Tokukai Sho! /-/-jAO issue, Tokukai Akira! ! -4
24tOr issue, Tokukai Sho! J-/$4 (J/1 issue, JP-A-Sho!≠-1007/7 issue or JP-A-KAI 3μ=irzrs
Physical ripening can also be carried out in the presence of thioethers and thione compounds described in No. r, etc.). This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pHt during grain formation. For more information, please see Photography Science.
and Engineering (Photographic
5science andgnglnearlng
) Volume, l! Its pages (4 pages); Journal of Photographic Science (Jour
nal of Photo-graphic 5
science), Volume 72, 2 #J~Jzi pages (
/Pj-tei), U.S. Patent No. 3. ≦! ! , 3ri1 and British Patent No. 1,4413,74c1.

Furthermore, as a monodisperse emulsion, silver halide grains with an average grain diameter of approximately 0.001 microns are used, and at least P! Emulsions in which the weight percent is within ±uO% of the average grain diameter are typical. Average particle diameter is 0.2! - Comicron and at least 1 or (number of particles)
At least Ri! An emulsion in which the number of silver halide grains is within a range of ±20% of the average grain diameter can be used in the present invention. A method for producing such an emulsion is described in U.S. Patent No. 3. ! 7≠
.

No. t, No. J, t! ! ,! and British Patent No. 1,4/L/J, 7441.

Also, Tokkai Shoda R-Rtoo issue, same! /-Jri0 core issue,
same! /-4JOri No. 7, same! ! -/37/33 No. 7
44-44112/, same j4A-4944/ri, same 1l-37tJj, same! Monodisperse emulsions such as those described in Japanese Patent No. t-39931 can also be preferably used in the present invention.

Furthermore, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (
Gutoff, Photographic Science
nce and Englneeering), 1st
Vol. 4' Ir ~ J j 7 pages C1970):
U.S. Patent No. 4g, Da 3 Da, Coco No. 6, Da, 4411,
No. 310, same da, 33. O≠ No. 4. ≠Jri, 1
No. 20 and British Patent No. J, //co, l! It can be easily prepared by the method described in No. 7, etc. When using tabular grains, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in the previously cited U.S. Pat. It is being

The crystal structure may be uniform, or the inside and outside may have different halogen compositions.1. It may have a layered structure. These emulsion grains are based on British Patent Nos. I, O core,
/ Reference No. 3, U.S. Patent No. 3. ! No. 01.041, No. 44,
14444! , No. 177 and Tokugansho! t-2φr da 6
It is disclosed in the following issue.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are described in US Pat. ? 0Q issue, same≠, 4Lt
No. 3!3, British Patent No. 2,031.7F-, U.S. Patent No. 3, No. 3 Hiroshi, No. 622, same da, 3 J, 4L71
No., same da.

-33, 10/No., Dohiro, Section 4J, No. 017, Same J,
41 &, ri j, No. 2, same J, r! No. 12,067, Japanese Patent Application Laid-Open No. 162!440, etc.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be coexisting.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

In order to remove soluble silver salts from the emulsion before and after physical ripening, washing with water, flocculation sedimentation, ultraleakage, etc. are performed.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

The additives used in such processes are based on the research and research mentioned above.
Disclosure &/76 Hiroj (/76 December 2017)
and the same constitution/Ir7/l (/7th year//month), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD17AltJ RD117/l.

1 chemical sensitizer ko 3 sada grit sada right column 2
Sensitivity increasing agent Same as above 3 Spectral sensitizer, page 23 - λμ 14 Right column - Super sensitizer
6 Data right column 4 Brightener 2≠Page 5 Anti-fogging agent Cog-25 Page 25 Blurring right column and stabilizer 6 Light absorber, Fuco! ~KoAtX 4 Narisada right column~
Ilter dye 1. Page 10 left column ultraviolet absorber 7 Stain inhibitor -J Tei right page 120 left) Right column 8 Dye image 1 elephant stabilizer Ko! Page 9 Hardener page Tri page pressure column 1G
Binder Page 27 Same as above 11 Lubricant for plasticizing Core page 410 right column 12 Coating aid, Table 27 Page 27 Same as above Surface activator 13 Statec anti-same page 27 Same as above Various color couplers can be used in the present invention. A specific example is the research disc a-jer A/7 mentioned above.
It is described in the patents listed in j 4tJ, ■-C to G. As dye-forming couplers, the three primary colors of the subtractive color method (
That is, couplers that give yellow magenta and cyan) by color development are important, and specific examples of diffusion-resistant, hydrophobic, ≠ equivalent or 2-equivalent couplers can be found in the aforementioned Research Disk A-Jar 4/7J4 (j , VI[-C
In addition to the couplers described in the patents described in Section D and D, the following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a pallast group. Specific examples include U.S. Patent No.
No. 4407,210, same No.

17! , No. 0J-7 and No. 3. -4! r, 106
It is written in the number etc. The use of two-equivalent yellow couplers is preferred for the present invention, as described in U.S. Pat.
lya No. J, ll-417. P2r No. 3.
33. J-0J and Hiroshi No. 022゜bu20, etc., the oxygen atom separation type yellow couplers, Japanese Patent Publication No. 5R-TO7IY, U.S. Patent No. ≠, ≠0/
, No. 711, No. 3, Colo. 02p, 几D/10
! ! (1972≠Mon), British Patent No. 1. ≠2! , O.J.
No. O, West German application publication cylinder 2. Koji, Ri No. 17, Koji No. 1,
Kot/, 3bu No. 7, same gko, 3kota,! ! No. 7 and No. 2≠33. Typical examples include the nitrogen atom separation type yellow couplers described in r/co.

The α-pipal aylacetanilide coupler has excellent color fastness, particularly light fastness, while the α-benzoylacetanilide coupler provides a high color density.

The magenta coupler that can be used in the present invention is preferably a hydrophobic indacylon or cyanoacetyl coupler having a pallast group! -Pyrazolone type and pyrazoloazole type Kab 2- can be mentioned. , j-pyrazolone-based couplers in which J-1i'7: is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue and coloring density of the coloring dye, and six representative examples thereof are:
U.S. Patent No. λ, 3//, Or2, No. 3413,
No. 703, No. ko, buoo, yrr, No. 2,901
, No. 173, No. J, Itco, No. 633, No. 3. /!
Co, No. t96 and No. 3,936,01! It is written in the number etc. Two equivalents! - As the leaving group of the pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat.
, the arylthio group described in No. 7 is particularly preferred. It also has a pallast group as described in European Patent No. 73°AJ4! - Pyrazolone couplers provide high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3.061 and μ32, preferably U.S. Pat. No. 3.72! , pyrazolo (z #' -C) (' t
J, 4()) Liazoles, Research Disclosure, = f; J4t, 220 (/7i'1 year as month)
Pyrazolotetrazoles and Research Disclosure described in JP-A No. 1sO-33112, &
Colco JO (/Yr Kou June) and Tokukai Sho tO-IA
J6! Examples include pyrazolopyrazoles described in No. Imidazo(/,J-b)pyrazoles described in U.S. Pat.
/ri, r j Pyrazolo (/, j-b
)(/,!,≠] triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant 7-tall and phenolic couplers, as disclosed in US Patent No. 2. ≠7≠.

No. 223, preferably the naphthol couplers described in U.S. Patent No. ≠, 0! Ko, Ko No. 12, Same No. μ.

Typical examples include the oxygen atom-eliminating type two-equivalent naphthol couplers described in No. 233 and No. 44,2, No. 200. Further, specific examples of phenolic couplers include U.S. Pat.
No. 1, No. J, 772. /62nd issue, same issue, rri! ,1
It is described in No. 24 etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic cyan coupler having U.S. Pat. No. 2,772,142;
Same No. J, 7! r.

No. 301, No. μ, / Koro, No. 3, No. 6, No. μ.

J3 Hiroshi, No. 0//, No. 3 Core, No. 173, West German Patent Publication No. 3,322,7 Kota and European Patent No. 12/
, 361, etc. -Diacylamino-substituted phenolic couplers and U.S. Patent Nos. J, 444, Yumi, I, No. 22, Hiroshi, No. 333, Tatata, No. μ, ≠
! ／ 、! ! It has a phenylureido group at the 11th position and is described in No. These include phenolic couplers having an acylamino group at the - position.

European Patent No. 141. Naphthol listed in Bukoro A issue! Cyan couplers substituted with a sulfonamide group, amide group, etc. at the − position also have excellent color fastness, and
It can be preferably used in the present invention.

In order to correct unnecessary absorption of color pigments, it is preferable to use a colored coupler in combination with a color negative sensitive material for photographing to perform masking. U.S. Patent No.

/43,470 and Tokuko Akira! Yellow-colored magenta couplers described in US Pat.

/31,2! r and British Patent No. 1, /4LJ
.

Typical examples include the magenta-colored cyan coupler described in No. 341 and the like. Other colored couplers are from the aforementioned Research Disclosure, A/744A7.
, described in sections ① to G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
US Patent No. Hiroshi, JAM, 437 and British Patent No. 2.
/2! ,! Specific examples of magenta couplers are given in European Patent No. 26,170 and West German Application No. 3,2.
No. 3≠, No. 533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,4Lj/, 1
No. 20 and No. 1A, oro.

! It is described in the // issue. Examples of polymerized magenta couplers are described in British Patent No. 2,10,773 and US Pat. No. A,367.212.

Couplers that release all photographically useful residues upon coupling can also be preferably used in the present invention. As the DIR coupler that releases a development inhibitor, the patented couplers described in the aforementioned Research Disclosure, &17/;

A preferred combination with the present invention is JP-A-Sho! 7-
/j/94# is the developer deactivation type: U.S.A.
Timing type that is numbered six times: Tokugansho! Ta 3 live! 3
A particularly preferred one is the reaction type represented by No. JP-A-Sho! 7-/Jl ≠ No. 1, same t-co/7-ri 3λ,
Special request! ? -7j≠7hiro, same Jr., -122/tago,
The same j tar r here/Hirogo and the same! Developer deactivated type DIR Kagura and Tokuhan Shoj described in Tata O≠3r etc.
This is a reactive DI coupler described in Patent No. 324jJ.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkaline dispersion method, preferably a latex dispersion method, and preferably an oil-in-water dispersion method. It can be mentioned as follows. In the oil-in-water dispersion method, the boiling point is 77! After dissolving in either a high-boiling point organic solvent of C or higher and a low-boiling point so-called auxiliary solvent alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high-boiling organic solvents are U.S. Pat.
It is described in Ko, No. 027, etc.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of latex dispersion methods, effects and impregnated amounts of latex are given in U.S. Pat.

No. 363, West German Patent Application (OLS) No. 2. Iμl.

No. 274L and No. 274L. ! +L/, No. 230, etc.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenols as color antifogging agents or color mixing inhibitors. It may also contain derivatives.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Bu-hydroxychromans! -Hydroxycoumarans, spirochroman fi, p-alkoxyphenols,
Typical examples include hindered phenols centered on bisphenol at, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the heptaenolic hydroxyl group of each of these compounds. It is mentioned as. Further, metal complexes represented by (bissalicylaldoximide) nickel complex and (bis-N,N-dialkyl ditheocarpamato) nickel complex can also be used.

The invention is also applicable to multilayer, multicolor photographic materials having at least λ different spectral sensitivities on the support.

Multilayer natural color photographic materials usually consist of a red-sensitive emulsion on a support.
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The arrangement of these layers can be arbitrarily selected as required. A preferred layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side, or blue-sensitive, red-sensitive, green-sensitive from the support side. Further, each of the above emulsion layers may be composed of λ or more emulsion layers having different sensitivities, or two emulsion layers having the same sensitivity.
A non-sensitive layer may be present between the two or more emulsion layers. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used in some cases. You can also do it.

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with auxiliary layers such as an S-holding layer, an intermediate layer, a filter layer, an antihalation layer, and a pack layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion and other layers are made of a usable support such as glass film, paper, or cloth, or glass, ceramic, etc., which are commonly used in photographic light-sensitive materials.
Applied to a rigid support such as metal. Flexible supports (N) include films made of cellulose or conductors (cellulose nitrate, cellulose acetate, cellulose acetate butyrate, etc.), synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), and baryta. paper coated or laminated with a layer or an α-olefin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored with dyes or pigments. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion 1→ etc.

The surface of the support may be subjected to gummy discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods can be used, such as a disk coating method, a roller a7f5 method, a curtain coating method, and an extrusion coating method. U.S. Patent No. 2,411 as appropriate.
Kota μ issue, same No.-, 741, futa No. 7, same No. J, jJ
J,, No. 1211, same No. J, J-Or, Tada 7
Multiple layers may be applied simultaneously using the coating methods described in the above.

The color photographic light-sensitive material according to the present invention is described in the above-mentioned Research Disclosure, Mu/74≠3, page r-a, and the same, Mu/17/l, page 4!1, left column to right column. It can be developed by a conventional method.

When the silver halide photographic light-sensitive material of the present invention is a black-and-white light-sensitive material, a black-and-white development and fixing step is carried out, when it is a color light-sensitive material, a color development, bleaching and fixing step is carried out, and when it is a color reversal light-sensitive material, a black and white development step is carried out. - Reversal, color development, brightening, and fixing steps are performed.

In the case of a color reversal photosensitive material, a known developing agent can be used for the first developer (black and white development) used in the present invention. -Pyrazolidone fA (
/-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), l-phenyl-3-pyrazolines, ascorbic acid, and the /- ,−
13. A heterocyclic compound in which a ≠-tetrahydroquinoline ring and an intrene ring are condensed can be used alone or in combination.

Kurohakugen 1* solution may contain other preservatives (for example,
sulfites, bisulfites, etc.), buffering agents (e.g. carbonates, boric acid, borates, alkanolamines), alkaline agents (
(e.g., hydroxides, carbonates), solubilizers (e.g., polyethylene glycols, esters thereof), pH adjusters (e.g., organic acids such as acetic acid), sensitizers (e.g., quaternary ammonium salts), A development accelerator, a surfactant, a toning agent, an antifoaming agent, a hardening agent, a viscosity imparting agent, etc. can be contained.

The first developing solution used in the present invention must contain a compound that acts as a silver halide solvent, and the above-mentioned fQ salt added as a preservative usually plays this role. The sulfite and other silver halide solvents that may be used include, specifically, 8CNSNaSCN, 803, N
a2s03, K2820. , Na2S20. , K2S2
Examples include O5, Na, 8.03, and the like.

In addition, a development accelerator is used to impart a development accelerating effect, and in particular, as disclosed in JP-A No. 17-63110, IftI'i
! The compounds represented by the following general formula (A) described in - may be used alone or in combination of two or more, and further, the above silver halide solvents may be used in combination.

General formula (A) 22+5-R21) d-8-R22 Before using these silver halide solvents, if too little is used, development progress will be slowed, and if too much is used, fog will occur in the silver halide emulsion. Therefore, there is a preferred amount to be used, but the amount can be easily determined by those skilled in the art.

For example, 5ON- is o, oo, r~0.
02 mol, especially o, oi to 0.0/j mol, and 5032- is o, oj to 1 mol, especially 0
, 1 to 0.1 mol.

When the compound of formula (A) is added to a black and white developer, the addition needle is preferably per developer per liter! ×1
0-6 mok ~ jX/ 0-1 mole, more preferably /
×10 mol to 2×10 mol.

The pI-1 value of the developer solution prepared in this manner is selected to be sufficient to provide the desired density and contrast, but ranges from about t,j to about /1. ! It is desirable that it be in range H.

In order to carry out sensitization treatment using such @l development, usually,
It is sufficient to extend the time up to about three times the standard processing time.

If the treatment temperature is raised at this time, the extension time for the sensitization treatment can be shortened.

The fogging bath used in the inversion step can contain a known fogging agent. That is, stannous ion-organophosphate acetate (US Patent No. 3.Al1゜Corr2Mei1\I!
B), stannous ion organic phosphonocarboxylic acid acetate (
Special Public ShojJ-,? jJ/A publication), stannous ion-
Aminopolycarbon #s1 [(British Patent No. 1.
stannous ion complex salt borohydride compounds such as (U.S. Patent No. 7);
Multi-ring amine borane compound (UK #license No. 1, 0//, 0
The pH of the fogging bath (reversal bath) using a boron compound such as No. 00 Specification Co., etc. ranges over a wide range from the acidic side to the alkaline side, and is preferably pH 2 to /2, preferably 2. ! It is preferably in the range of 3 to 10X, preferably 3 to 10X.

Color expression 17 used in the present invention! The solution has the composition of a typical color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are p-phenyl diamine derivatives as shown below. N, N
-diethyl-p-phinyl diamine, koamino-yo-diethylaminotoluene, koamino! -(N-ethyl-N-laurylamino)toluene, u-(N-ethyl-N-(β-hydroxyethyl)aminecoaniline,
Comethyl-μ-[N-ethyl-N-(β-hydroxyethyl)amine coaniline, N-ethyl-N-(β-methanesulfamidoethyl)-3-methyl-≠-aminoaniline, N-(J-amino -Yo-diethylaminophenylethyl) methanesulfonamide, N,N-dimethyl-
p-Finyl diamine, U.S. Patent No. 36!4910, U.S. Pat. 2! Amino-3-methyl-N-ethyl-N-methoxyethylaniline, ≠-amino-3-methyl-N-ethyl-N-β-
Preferred representatives include ethoxyethylaniline, Hiro-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline, and salts thereof (e.g. sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.) This is an example.

The color developer may also contain other known developer component compounds. For example, alkali agents, buffering agents, etc. include caustic soda, caustic potash, soda carbonate, potassium carbonate,
Tertiary sodium phosphate or potassium, potassium metaphosate, borax, etc. are used alone or in combination.

Color developing solutions usually contain sulfites, which are used as preservatives.
For example, sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite) or hydroxylamine can be added.

If necessary, any development accelerator can be added to the color developing solution. For example, US Pat. Various pyridinium compounds and other cationic compounds, cationic pigments such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate,
Special Publication Akihiro≠-210Hiro, U.S. Patent No. 2133220
No. specification, U.S. Patent No. 2,131,132, Kota t
o270 specification, same co! Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. 77/27, organic solvents and organic amines, and ethanol described in Japanese Patent Publication No. 77/27, Belgian Patent JIr, 2rt No. Amine, ethylenediamine, jetanolamine, etc., etc., F, A, Mason (L, F.

A, Mason), 'Photographic Brosse'/7g C Chemistry
rocessing Chemistry)”, No. μ
Pages 0 to IA3 (published by Focal Press, /9tA)
The accelerators described in can be used.

Furthermore, the color developer may contain aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydrodimethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, etc. as a water softener. can.

Competing couplers and compensating developers can also be added to the color developer.

Citrazic acid, J acid, H acid, etc. are useful as competitive couplers.

As a compensating developer, p-aminephenol, N-benzyl-p-aminephenol, l-phenyl-3-pyrazolidone, etc. can be used.

The pH of the color developing solution is preferably in the range of about t to /3. The temperature of the color developing solution is selected within the range of 0.degree. C. to 70.degree. C., preferably 30.degree. C.-40.degree.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As bleaching agents, compounds of polyvalent metals such as iron (III), cobalt (IV), chromium (Vl), and copper (II), peracids, quinones, and nitrone compounds are used. For example, 7-erycyanide, dichromate, organic complex salts of iron(In) or cobal(III), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, l
, 3-diamino-pro/l-nortetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. can. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (
nl) Sodium and iron(I) ethylenediaminetetraacetate
ll) Ammonium is particularly useful. Aminopolycarboxylic acid chichi(III) complex salt has -
Also useful in bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, US Pat.
IOT issue bulletin, special public show 11! It is also possible to add various additives including the bleaching accelerator described in Japanese Patent No. 1134 and the like.

The fixing bath of the present invention contains 3 ot/(3 ot/(
Used at a concentration of 1-200t/l, and other stabilizers such as Vζ, sulfites, isomeric bisulfites, hardeners such as potash alum, acetates, borates, phosphates, carbonates. , etc. may be included. The pH of constant Sg is 3 to 10, more preferably t.

After development, bleach-fixing, or fixing, a washing treatment or stabilization treatment is usually performed.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A No. 7-17≠3 instead of the water washing step. In the case of this step, a countercurrent column of a tank is required. Each strain compound is added to this stabilizing bath for the purpose of stabilizing the image. For example, various buffers (e.g., borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water monomer) for adjusting membrane pH (e.g., pH 3-1). Examples include (using a combination of carboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (
Various additives such as benzisothiazolinones, isothiazolones, Hiroshithiazolinebenzimidazoles, chlorogenated phenols, etc.), surfactants, fluorescent brighteners, and hardening agents may be used. Two or more compounds having the same or different objectives may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

In addition, stabilizers such as sulfites and isomeric bisulfites,
A hardening agent such as potash alum, a pH buffering agent such as acetate, borate, phosphate, carbonate, etc. may be included. The pH of the fixer is 3 to 10, more preferably! It is ~ri.

(Examples) Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example A As a sample, a multi-colorless light-sensitive material Ioi was prepared on a tri-acetyl cellulose film support, consisting of each layer having the composition shown below.

1st layer; anti-halation layer black colloidal silver 0.11
Gelatin containing 17 m2, 1- second layer; middle layer,! -G-t-pentadecylhydroquinone...
・・・・・・・・・ o, try/m2 coupler C-3
・・・・・・・・・ 0. //? 3rd gelatin layer containing /m2; 1st red-sensitive emulsion Bitten silver iodobromide emulsion (S iodide ≠ morch, average grain size O0μμ)...
・・Silver price cloth! (Same below) 0.72? /m2 sensitized color cord A
・・・・・・・・・ θX10 for 1 mole of starvation
Molar sensitizing dye B......j per mole of silver
, OX/ 0 mol sensitizing dye C ≠ per 1 mol of silver
CoXIO mole sensitizing dye D...3 per mole of silver
, O×10 molar coupler c-a -----・-o , ori3y7
tn” coupler C-Yu ・・・・・・・・・ 0.3
1917m” coupler C-a ・・・・・・・・・
Gelatin containing 0.01 t/m2 [- μth layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・
/, 017 m2 (10 moles of silver iodide, average grain size i, oμ) Sensitizing dye A ...... 7, tXlo-5 moles per mole of silver Sensitizing dye B ... ...... Co, Co x 10-5 moles per mole of silver Sensitizing dye C...3.
0X10-'mono sensitizing dye D ・・・・・・・・・ 2 for 7 moles of dye
．． 2×10-5 molar coupler C-≠ ・・・・・・・・・・・・ 0. /
f/rn2 coupler C-j ------0,04
/? /m2 coupler C-7...--o, o Hiro At/
Gelatin layer containing m2; Third red-sensitive emulsion J- Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・
/, yf/m2 (silver iodide 10 mol, average grain size /, jμ) Sensitizing dye A ・・・・・・・・・ @ 1.0×10 mol per 1 mol Sensitizing dye B ・・・・... Co, ≠ × 10"-5 moles per mole of silver sensitizing dye C ... - J, J × per mole of silver
10 mol sensitizing dye D... λ per 1 mol of silver
,≠×10 Molar coupler C-7・・・・・・・・・ 0.3227m
6th gelatin layer containing 2 couplers C-/7 and 0.001 f/m2; 7th intermediate gelatin layer; 1st green-sensitive emulsion, no major silver bromide emulsion... ... o,
zzy7m” (3 molti silver iodide, average grain size 0.2
μ) Sensitizing dye G: 3, r'pe, to mole per mole of silver Sensitizing dye E: 1 per mole of silver
．． 1 x IO molar coupler C-r ・・・・・・・・・ O, Kota S
' / tn 2 Kazorah C-j ・・−・−・−
0,044t/m” coupler C-10・0.0!i
f/m2 coupler C-//-0,0! If/m'' containing gelatin layer; Second green-sensitive emulsion 1-Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・
/, 097 m2 (t mol of silver iodide, average grain size /
, spherical particles of μ μ) Sensitizing dye G ・・・・・・・・・2 per mole of silver
．． 7×10 moles Sensitizing dye E ・・・・・・・・・1 per 91 moles
, /×10 molar coupler C-r ・−・−・−0,,2! t7m”
Coupler c-s -・-=o, oi3t7m" coupler C-10-0,00917m2 coupler C-/
/-0,0//? /m" gelatin layer; third green-sensitive emulsion layer; silver iodobromide emulsion; third green-sensitive emulsion layer; silver iodobromide emulsion;
-, oy7m” (silver iodide t mol 儂, average grain size/
, 1μ spherical particles) Sensitizing dye G ...... s per mole of silver
, oxio mole sensitizing dye E ...... 1 for 91 moles
, Ko×lO molar coupler 〇−j ・−・−0,0Or? /m2 coupler C-/co..." 0.0!f/m2 coupler c-tr-o,oo/17m" Gelatin layer io layer; Yellow filter I- Yellow colloidal silver...・・・・・・ 0.0≠
? /m2- j-di-t-pentadecylhydroquinone 11th layer of gelatin layer containing 0.03/f/m2; 1st curved emulsion layer Silver iodobromide emulsion...・・・・・・・・・・・・ 0.
Three? /m2 (iodide 9Mj molar rolling average particle size Q, u
μ) Coupler C-/J ・-・-o, Arf/m2
Kagura C-/4C-・-0,0jf/m2 Ka'zt
-c-7y -... Gelatin layer 1st layer containing o, oitt7m''; 2nd back emulsion layer Silver iodobromide emulsion 0.
Kota f/m2 (silver iodide io mole, average grain size 1.
0 μ) Sensitizing dye F ...... λ, co x lO mole coupler C-/J ...... 0.221/m for 1 mole of silver
Gelatin layer 13th layer containing 2; Fine grain emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・
0. μ? /m2 (silver iodide 2-T: ruti, average grain size 0./!μ) Gelatin layer 1st layer; 3rd evening-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・ 0.
17 m'' (silver iodide/l' molar average grain size 2
．． 3μ) Sensitizing dye F ...... 2.3 x 10 mole coupler per 1 mole of silver C-/J -------0,/lit 7m
Gelatin layer 1 containing 2 couplers C-/j ・0.00197m2! Laminate 1st protective layer UV double absorber C-/・----0,11797m
2 Ultraviolet absorber C-2... O, Co-y 7
Gelatin layer 74th layer containing m 2; second protective layer polymethyl methacrylate particles (diameter /, !μ)・old・
・・・・・・ 0.0! In addition to the above composition, each gelatin layer containing t/m2 contains a gelatin hardening agent, C-/
4 and a surfactant were added. The sample prepared as described above was designated as sample 10/.

The compounds used to prepare the sample are shown below.

C-/ x:y=7:J (heavy lid ratio) -J C-μ 0CH2CH2So□CH3 −z t-C,H,1 -t C-/.

α 1:'(Q4- C-// α C-/J Sensitizing dye Human sensitizing dye B Sensitizing dye C (CH2) 380 a N a Sensitizing dye Sensitizing dye E Sensitizing dye F Sensitizing dye G h Preparation of sample IOλ to sample ilr Sample 10 except that the compound shown in 1st fi and f shown in 1st fi were added to the third layer and third layer of sample 10/.
Samples IO2~//1 were prepared in exactly the same manner as in Example 1.

For these samples /DI~//1, one part was exposed to red wedge light, and the other part was exposed to white wedge light (red +
green + blue original) t- given. The amount of red g light at the time of daylight,
The exposure area during red exposure was the same and rare.

Each of these exposed samples was subjected to color development using a color developer.

The development process in this case was carried out using 3r@C as described below.

Compare the red light w, the original cyan and the cyan exposed to white light,
It can be said that the larger the light amount difference Δ1ogE is at 1 between the densities o and t, the larger the interimage effect is.

Graininess (R, MS granularity Ii) is the standard deviation of the concentration fluctuation that occurs when scanning with a microdensitometer.
000 times the value.

Color development 3 minutes lt seconds Bleached white 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time μ minutes O seconds Wash with water for 3 minutes! seconds Safe, stable, 1 minute 03 seconds The treatment g composition used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid/, 0fl-hydroethylenetriidene/.

l-diphosphonic acid λ, oy sodium sulfite μ, ot potassium carbonate
! 0. Ofpotassium bromide
1. Hiro? potassium iodide
/, 3~hydroxylamine sulfate λ
, $2≠-(N-ethyl-N-β-hydrodiethylamino)-2 monomethylaniline sulfate ≠,! ? Add water i, olpHlo, 0 white liquor ethylenediaminetetraacetic acid ferric ammonium salt ioo, ot ethylenediaminetetraacetic acid disodium salt 10. Of ammonium bromide izo, ot ammonium nitrate io, or add water
/,01pH6,.

Fixer ethylenediaminetetraacetic acid disodium salt /, Of sodium sulfite ≠, ot ammonium thiosulfate aqueous solution (70 whispers) / 7j, 0ytJ sodium bisulfite ≠, tf add water
1.0ip'HA, 4 Stable formalin (uo%) λ, Oyd polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3? By adding water /, O1 Compound A Compound B From these results, the present invention provides superior interimage effect and graininess compared to the comparative example, and also has a lower Dm
It can be said that in is low.

Example Next, Sample 20/ was prepared by coating the first to seventh layers on a triacetate film base in the following order.

1st layer; antihalation layer (gelatin layer containing dotted colloidal silver).

2nd layer; Gelatin middle layer 2! - Dit ~ Octyl hydroquinone is dissolved in 100 Cc of dibutyl phthalate and 10 OCC of ethyl acetate, and the emulsion obtained by stirring at high speed with 9 in a water bath solution of lOs gelatin is used as a fine grain emulsion (particles) that is not chemically sensitized. Size 0.01.μ, 1 mol fk beautified silver emulsion)/10% gelatin with anchor/.

Silver n
o, ≠t/m).

3rd layer: low-sensitivity red-sensitive emulsion layer 2-(hectafluo abutyramide)-y-(co'-(co'I4!'-di-t-aminophenoxy7)butyramide)-phenol 100f, which is a cyan coupler, 106 cc of tricresyl phosphate and 10 cc of ethyl acetate
Dissolved in 0cc,! The emulsion root obtained by stirring at high speed with a θ% gelatin aqueous solution (9) is mixed with a red-sensitive silver iodobromide emulsion (containing 70 tons of silver, gelatin A Off, and iodine content is μmol), and a dry film is formed. It was applied to a thickness of lμ. (Amount of silver 0.≠P/m) μth layer: Highly sensitive red-sensitive emulsion layer cyan coupler RAL-KOR (heptafluorobutyramide) -1-(CO/-(,z",≠"-Z-t) -aminophenoxy)butyramide 1-phenol 100ff
) Red-sensitive silver iodobromide emulsion 114 (silver 70?, gelatin 401 , and the iodine content is 2 t mol %), and the dry film thickness is... μ
It was applied so that (scissors to, at/m) No. J
'Layer; Middle layer 21! - Di-t-octylhydroquinone is dissolved in 10 OCC of dibutyl 7-thalerate and 10 QCC of ethyl acetate, and an aqueous solution/squeezed in 70% gelatin and stirred at high speed, resulting in emulsion 14, is mixed with 1# of 10% gelatin, It was applied so that the dry film thickness/μ was obtained.

6th layer; low green-sensitivity emulsion layer JOO? emulsion obtained in the same manner as the emulsion of the 3rd layer except that C-10, a magenta coupler, was used instead of the cyan coupler. 'f, green-sensitive silver iodobromide emulsion l# (silver 7
0? , gelatin 60? (contains iodine content of 3 molt)
to a dry film thickness of l.

It was applied to a thickness of 3μ. (Gin jko, ty7
m) 7th layer: Highly sensitive green-sensitive emulsion layer C-2 which is a magenta coupler instead of a cyan coupler
An emulsion 1000f obtained in the same manner as the emulsion of the third layer except that 1000f was used was a green-sensitive silver iodobromide emulsion/14C silver 7
0t, gelatin 40? (with an iodine content of 1,000 mol %) and coated to a dry film thickness of 3.3 μm. (Silver to, ry/m2) Layer 1: Yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness of lμ.

2nd layer; low-sensitivity blue-sensitivity emulsion layer α-(
hivaloyl)-α-(/-benzyl-j-nitoxy-3
Emulsion 10009, which was obtained in the same manner as the emulsion for the third layer except that 1-dodecyloxycarbutylacetanilide was used, was mixed with a back-sensitive silver iodobromide emulsion l# (silver 709.Contains gelatin toy, has an iodine content of 7 mol%), and has a dry film thickness of 1. jμ
It was applied so that (Amount of silver 0.lhf/m”) 1st
O layer; Highly sensitive red-sensitive emulsion layer α-(
piparoyl)-α-(/-benzyl-!-ethoxy 3
-hydantoinyl) -2-10 low! - Emulsion 1oooy obtained in the same manner as the emulsion for the third layer except that dodecyloxycarbonylacetanilide was used, was mixed with the above-mentioned spherical silver iodobromide emulsion B/U (containing silver 70?, gelatin toy, iodine The content is 2.3 mol%) and the dry film thickness is 3μ.
It was applied so that (Silver II/ , / 17m2)
Eleventh Layer: Protective Layer The emulsion 114 of the ultraviolet absorber C-t used in Example 1 was mixed with lO tizelatin/9% and coated to give a dry film thickness of 2 μm.

1st J layer: Fine grain emulsion covered with the surface of the first protective layer (grain size O0lμ,
An aqueous gelatin solution containing polymethyl methacrylate particles (diameter /, !11, o, or f/m2) was coated to a dry film thickness of O0rμ.

Gelatin hardener C-/A and surfactant were added to each layer, respectively.

Preparation of sample -〇- ~ Coco O Add the compound shown in Figure 2 to the 3rd or 6th layer of sample -0/ to the layer shown in Table 2. The sample was prepared in exactly the same manner as sample 20/ except for
λλO4- was produced.

C - Co θ For these samples 201 to Coco O, a portion of each sample was subjected to green wedge exposure at a different location, and a white wedge exposure (red + edge + actual color source) was applied to the other portion. The exposure amount of green light during white exposure was the same as the exposure amount of green light.

These exposed samples were subjected to the following development treatment.

Processing process Step Time Temperature First development Minutes 3r”c water washing
2 minutes 7 reversals 2 minutes
3r IC color development Minutes Adjustment Minutes Column White 6 minutes Fixed M
47 minutes Wash with water
μ minutes Stable 7 minutes
The composition of the room temperature drying treatment solution is as follows.

No.-Developer water 700
．． ! Trilo N, N, N-) phosphonic acid! Sodium salt J2 Sodium sulfite 20f hydroquinone monosulfone)
JOf sodium carbonate (l hydrate)
301/-phenyl #μ methyl, 4L- and droxymethyl-3 pyrazolidone, f beautifying potassium λ,! Potassium tateocyanate /, co? Potassium iodide (0,
/q6g) Add J Go water
1000m1 inverted liquid water 700
rttlnitro・N-N,N-trimethylenephosphonic acid・! Sodium salt 3 stannous chloride (l hydrate) 1yp-aminophenol. , /f sodium hydroxide
,rrglacial acetic acid
/jmg water full force day
1000 Go color developer water 700
m1 Nitrilo・N-N,N-)lytyrenephosphonic acid・j Sodium salt 32 Sodium sulfite 7f Sodium tertiary phosphate (/cohydrate) 362 Potassium bromide /i Potassium iodide (0.7% solution) Ta . dSodium hydroxide
3? Citrazic acid
/,! 2N ethyl-N-(β-methanesulfonamidoethyl)- 3m methyl-l-aminoaniline sulfate //? Ethylenediamine 32 Add water
1000atl adjusted liquid water 700
Sodium sulfite/comiethylenediamine/sodium tetraacetate (l hydrate), r? Thioglycerin. , glacial acetic acid
Add 3d water / 000
ml chain white liquid water f0
0ml Sodium ethylenediaminetetraacetate (cohydrate) JP Ethylenediaminetetraacetate iron (In) ammonium (-dihydrate) 1209 Potassium bromide 100? add water
1000d fixer water r 0
0 rig sodium thiosulfate IO,
Of sodium sulfite 1.02 Sodium bisulfite z, ot Add water 10100O stable liquid water 100
rd formalin (37 layers iii) j
, 0ILt Fuji Drywell (surfactant manufactured by Fuji Film ■) j , ad Water was added and the above sample was developed with the above developer for 1000rd. Green fF, magenta when exposed and magenta when exposed to white light were compared. , density/, the exposure amount difference Δ1ogE at 0 was measured.

It can be said that the greater the value of Δ1ogE, the greater the interimage effect.

Father, the MTF value of IO cycles/tn m was measured.

These introductions are shown in Table 2.

From these results, it is clear that, compared to the comparative example, the ink of the present invention provides an excellent interimage effect without lowering Dmax due to an increase in capri, and also provides improved sharpness.

Example 3 Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to prepare a silver iodobromide emulsion (Ag concentration = j mol %) with an average grain size of 0.7 μm. After desalting, a silver iodobromide emulsion was prepared by optimally sensitizing gold and sulfur with chloroauric acid and sodium thiosulfate.

Emulsion B (average grain size/Jμ AgI = 3 mol) was prepared in the same manner.

As a sample, a black-and-white photographic material was prepared on a cellulose triacetate film support, consisting of each layer having the composition shown below.

1st layer; low-sensitivity plate silver halide emulsion layer Emulsion A (coated silver i 197m) 2nd layer; high-sensitivity silver halide emulsion layer Emulsion B (coated silver wave -, !rt/m) 3rd layer;
Protective layer gelatin (1,3?/m ) Polymethyl methacrylate particles (diameter 7.7μ) 0.0
! In addition to the above composition, gelatin hardening agent C-74 was added to f/m2 valley and 1.
Added surfactant and thickener polystyrene sodium sulfonate. Sample 30/
And so.

These samples were exposed to light through a pattern for measuring graininess, and then subjected to the development process described below.

Developer (E) Metol 2f Sodium Sulfite 100? hydroquinone
! ? Zeratx! H20/
,! ! ? Add water and developer C
F) Metol Co-sodium sulfite 100f Hydroquinone
Tat Volax-zH20i
, z3p Potassium iodide A (O, /%) jd Add water /E Fixer ammonium thiosulfate Cooo, oy Sodium sulfite (anhydrous) 20.0? boric acid
! , 0? Ethylenediaminetetraacetic acid disodium 0. l? aluminum sulfate is, or sulfuric acid
or glacial acetic acid
22.0? add water
/, 0Il (pH adjusted to DA, KO) Black and white development was performed for 20@07 minutes using the above developer.

Graininess (RM8 granularity) is 1ooo of the standard deviation of the 5 degree fluctuation that occurs when scanning with a microdensitometer.
Displayed as double value.

Further, the sharpness was measured using the MTF value.

These results are shown in Table 3.

From these results, it is clear that the sample using the present invention has less capri and is superior in graininess and sharpness compared to the comparative example.

Patent Applicant Fujisha-X Film Co., Ltd. Procedural Amendment Showa JJ July Tsubo day

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, comprising at least one compound represented by the following general formula [I] and the following general formula [I]. A silver halide photographic material comprising at least one compound represented by formulas [II] and [III]. General formula [I] A-(Time)_t-X General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A in the general formula [I] means a redox mother nucleus, and it is not until it is oxidized during photographic processing that -(T
time)-_tX represents an atomic group that allows it to leave, and Time is a sulfur atom, nitrogen atom, or oxygen atom.
represents a timing group linked to, t is an integer of 0 or 1, and X represents a phenomenon inhibitor. In the general formula [II], R represents a straight-chain or branched alkylene group, a straight-chain or branched alkenylene group, a straight-chain or branched aralkylene group, or an arylene group, and Z
represents a polar substituent. Y is -S-, -O-, ▲ formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_1,
R_2, R_3, R_4, R_5, R_6, R_7, R
_8, R_9 and R_1_0 each represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or aralkyl group. X' represents -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -S-, and R
' represents a hydrogen atom or a substituted or unsubstituted alkyl group or alkenyl group, respectively. R'' represents a hydrogen atom or a group that can substitute this.M
represents a hydrogen atom, an alkali metal atom, an ammoniumyl group, or a group that cleaves under alkaline conditions. n represents 0 or 1, and m represents 0, 1 or 2. However, X'
When is -S-, m=0 is not included. l represents 4-m. In the general formula [III], R''' represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group, and Z' represents a hydrogen atom or a polar substituent. Y' is -S- , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents R_1_1, R_1_2, R_1_3, R_
1_4, R_1_5, R_1_6, R_1_7 or R
_1_8 represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or aralkyl group. n represents 0 or 1.